JPH0491003A - Mite controlling agent - Google Patents

Abstract

PURPOSE:To obtain a mite controlling agent, containing eugenol, methylisoeugenol or derivative thereof, etc., as an active ingredient with high safety for human bodies and especially useful for controlling mites of the families Dermatophagoidinae, Acaridae, Cheyletidae, etc. CONSTITUTION:A mite controlling agent containing 0.1-40wt.%, especially 0.5-40wt.% compound expressed by the formula (R is H, alkyl or aralkyl; X is CH2-CH=CH2 or CH=CH-CH3). The compound expressed by the formula is available from a wood oil ingredient prepared by extracting wood of Sciadopitys verticillata Sieb. et Zucc. with methanol, etc., or can also be chemically synthesized. The compound expressed by the formula is normally mixed with a solid carrier, a liquid carrier, a gaseous carrier, a surfactant, a film- forming agent and other adjuvants and prepared as a formulation such as an emulsion, a wettable powder, a dust, a granule, an aerosol, a fumigant or a poison bait to carry out treatment of TATAMI mats (a mat in Japanese life), carpets, sofas, FUTON (thick bedquilt), closets, warehouses, etc., by a method for spraying, coating, thermal volatilization, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention is directed to a control agent for insect pests such as Dermatophagoides mites, Dermatophagoides mites, and Thick mites, which occur in houses and are especially harmful.

[Prior Art] Dust mites sometimes occur in large numbers in homes, and are becoming a social problem as they cause childhood asthma, dust mite allergies, and dust mite bites.

Conventionally, methods such as treating tatami mats outdoors with sunlight have been used to combat mites, but the effects were insufficient, and with urbanization, it has become difficult to treat tatami mats with sunlight outdoors, so methods such as treating tatami mats outdoors with sunlight have been used. Various methods have been used recently, such as spraying insecticides on children, bedding, and carpets as mite control agents, and recently, aerosol spraying, high-frequency treatment, heating with a futon dryer, and use of insect repellent paper.

Conventionally, insecticides for controlling these indoor mites, such as Dermatophagoides mites, Dermatophagoides mites, and T. mites, include organic phosphorus compounds such as fenitrothion, fenithion, dichlorvos, and diazinon, and carbamates such as proboxal and carbaryl. Pyrethroid compounds such as resmethrin, phenothrin, and permethrin are known.

[Problems to be Solved by the Invention] However, many organic phosphorus compounds are generally highly toxic and have a unique odor, so problems have been pointed out when using them indoors as tick control agents. ing. In addition, many carbamate compounds are generally highly toxic (and have similar problems.Furthermore, although pyrethroid compounds are generally low toxicity, there are safety issues when using them in ways that often involve contact with the human body. There are restrictions on how it can be used, and it cannot necessarily be said to be sufficient as a mite control agent.

As described above, dust mite repellents are generally sprayed indoors on areas that come into direct contact with the human body, such as tatami mats, futons, and carpets, so it is highly effective as a mite repellent. Needless to say, it is particularly important that the toxicity to the human body be low.

That is, there is a need for a mite control agent that can be safely used without causing any toxicity problems even if it comes into direct contact with the human body.

However, such a mite control agent has not yet been found, and the reality is that the industry is looking forward to the development of such a mite control agent.

The purpose of the present invention is precisely in this respect, and is to provide a safe mite control agent that is highly effective in controlling mites.

[Means for Solving the Problems] Therefore, the present inventors conducted various studies in order to develop an effective tick control agent that solved the above problems.

As a result, they discovered that methylisoeugenol, a component in the oil obtained by solvent extraction from Kouyamaki tree wood, has acaricidal activity, and that these derivatives also have low toxicity and are available in many types. The present inventors have discovered that the present invention has excellent acaricidal activity against mites, and have completed the present invention.

That is, the gist of the present invention is as follows: General formula [wherein R represents a hydrogen atom, an alkyl group, or an aralkyl group]. X is -CH2-CHCH2 or -CH=CH-
Represents CH. The present invention relates to a tick control agent containing a compound represented by the following formula as an active ingredient.

Regarding the general formula, the alkyl group represented by R is:
It may be linear or branched, and examples thereof include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, 5ec-butyl, and hexyl. Preferred are methyl, ethyl, propyl and isopropyl.

Examples of the aralkyl group represented by R include phenyl groups in which the aryl group is unsubstituted or substituted with a methyl group, etc., and the alkylene group includes those having 1 to 2 carbon atoms. Specific examples of such alkylene groups include benzyl and phenethyl.

Specifically, the compounds exhibiting acaricidal activity of the present invention include eugenol, methyleugenol, ethyleugenol, n
-propyl or isopropyl eugenol, n-butyl or 5ec-butyl eugenol, benzyl eugenol, phenyl eugenol, 〇- or p-methyl phenyl eugenol, isoeugenol, methyl isoeugenol, ethyl isoeugenol, isopropyl isoeugenol, n-propyl isoeugenol , n-butylisoeugenol, hexylisoeugenol, benzylisoeugenol, phenylisoeugenol, 〇- or p-methylphenylisoeugenol, phenethylisoeugenol, and the like. These compounds have been used as food additives for many years because they have low toxicity and aroma as natural essential oil components and derivatives thereof. Therefore, it is highly safe and can be used with confidence in controlling mites on tatami mats, carpets, bedding, etc. at home. Another advantage is that it can be easily chemically synthesized.

The mite control agent of the present invention can use a refined oil component obtained by extracting the wood of Aspergillus elegans in the family Aspergillus family using a solvent such as methanol or hexane by a conventional method. Alternatively, it can be purified and separated from ylang-ylang oil by rectification or other methods (isoeugenol).

In addition, the compound represented by the general formula can be easily produced by chemical synthesis, but for example, Be1lstein
6, I 459, ll916-918. It can be easily produced by the method described in or a method analogous thereto, and the compound synthesized in this way can be used. In addition, among the compounds represented by the general formula,
Some are commercially available; for example, for isoeugenol, one manufactured by Wako Tsumugi Pharmaceutical Co., Ltd. may be used.

The mite control agent of the present invention may contain a single compound or a mixture of two or more of the compounds represented by the general formula. Examples include combinations.

In addition, the mites targeted in the present invention include, for example, Dermatophagoides mites, such as Dermatophagoides nigricans, Dermatophagoides nigricans, Dermatophagoides nigricans, Dermatophagoides nigricans, Dermatophagus erectus
The mites are mainly indoor dust mites, such as the stag mite and the foot mite.

The mite control agent of the present invention contains a compound represented by the general formula,
It may be used as is without adding any other ingredients, but
Typically solid carriers, liquid carriers, gaseous carriers, surfactants,
It is mixed with film-forming agents and other formulation auxiliaries and used in formulations such as emulsions, irrigation agents, powders, granules, oils, aerosols, aerosols such as foraking, liniments, poison baits, etc. In addition, in the case of methylisoeugenol, 5
Since it contains ~IO% by weight, Kouyamaki wood oil can be used as it is or diluted with a solvent such as acetone, xylene, white kerosene, etc. It is also possible to use it by adding it to other plant essential oils such as cypress oil collection, wood oil, cedar oil collection, wood oil, cypress oil collection, wood oil, etc.

Examples of solid carriers used in formulation include diatomaceous earth, acid clay, carrion clay, ammonium sulfate,
Examples include fine powders or granules such as talc and corn cob flour. Examples of liquid carriers include aliphatic hydrocarbons such as kerosene and kerosene, aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene, halogenated hydrocarbons such as dichloroethane and carbon tetrachloride, methanol, ethanol, Alcohols such as isopropanol, ethylene glycol, cellosolve, ketones such as acetone, methyl ethyl ketone, cyclohexanone, tetrahydroisophorone, ethers such as diethyl ether, dioxane, tetrahydrofuran, esters such as ethyl acetate, acetonitrile, isobutyronitrile Examples include nitrites such as dimethylformamide, acid amides such as dimethylacetamide, vegetable oils such as soybean oil and cottonseed oil, and dimethyl sulfoxide. As a gaseous carrier -
Examples include chlorofluorocarbon gas, LPG, dimethyl ether, and the like. Examples of surfactants include anionic surfactants such as alkyl sulfate ester salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, and naphthalene sulfonic acid formalin condensates used for emulsification, dispersion, and wet spreading. , polyoxyethylene alkyl ether,
Examples include nonionic surfactants such as polyoxyethylene polyoxypropylene block copolymers and sorbitan fatty acid esters. In addition, examples of coating film forming agents include cellulose derivatives, vinyl resins, alkyd resins,
urea resin, epoxy resin, polyester resin,
Examples include urethane resin, silicone resin, acrylic resin, and polyvinyl alcohol. Other formulation adjuvants include lignin sulfonate, alginate, polyvinyl alcohol,
Examples include gum arabic, molasses, casein, gelatin, CMC (carboxymethyl cellulose), pine oil, agar, etc., and examples of stabilizers include alkyl phosphates such as PAP (isopropyl acid phosphate) and TCP (tricresyl phosphate), vegetable oil, epoxidized oil, the above-mentioned surfactant,
BIT.

BE (antioxidants such as A, fatty acid salts such as sodium oleate and calcium stearate, methyl oleate,
Examples include fatty acid esters such as methyl stearate.

The method of using the mite control agent of the present invention is to treat bedding such as tatami mats, carpets, pine mattresses, sofa-1 futons, pillows, closets, warehouses, etc. by methods such as spraying, spraying, coating, fogging, heating evaporation, and installation. It is used in some cases. Furthermore, the mite control agent of the present invention can be used in combination with various acaricides, synergists, pest repellents, rat repellents, fungicides, fungicides, fragrances, colorants, and the like.

In the mite control agent of the present invention, the compound represented by the general formula is contained in the formulation as an active ingredient in an amount of usually 0.1 to 40% by weight, preferably 0.5 to 40% by weight. If it is less than 0.1% by weight, the acaricidal effect will be low, and if it exceeds 40% by weight, the shape of the preparation will be poor when mixed with other substances, which is not preferable.

The amount of the mite control agent of the present invention to be used depends on its dosage form and application target.
Appropriate selection is made depending on the application method and application location. for example,
When using in the form of oil or spray, the effective concentration is 1.
It is used in the range of 0.5g to 10g per eye. Also,
Emulsions, aquariums, etc. containing the compound of the present invention are generally diluted with water to reduce the active ingredient concentration to 0. Preferably, a diluent of 1 to 5% by weight is used.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples and Test Examples, but the present invention is not limited to these Examples in any way.

In the following examples, "part f" indicates parts by weight.

Preparation Example 1 Preparation of methylisoeugenol Sodium hydroxide2. Og (0.05 mol) 20
Isoeugenol (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) in a solution dissolved in g of water 8. Add 2-1 g (0.05 mol) and
Stir for 10 minutes at ~5°C and add 7.56 g of dimethyl sulfate (0
,06 mol) over 30 minutes at 5-20°C,
Thereafter, the mixture was heated at 70 to 85°C for 3 hours, cooled, and extracted with benzene. Next, the benzene solution was washed with saturated brine and dried over anhydrous sodium sulfate. After concentrating the benzene solution with an evaporator, column chromatography (silica gel, hexane: ethyl acetate 5:
I) Separation and purification yielded 7.03 g of methyl isoeugenol (yield 79%) as a colorless oily mixture of cis and trans.
(b, I), 270°C, d=1.05).

Preparation Example 2 Preparation of ethylisoeugenol Potassium hydroxide 4. 21 g (0,075 mol)
12.32 g (0,075 mol) of isoeugenol (manufactured by Wako Tsumugi Co., Ltd.) and 9.45 g (0,075 mol) of diethyl sulfate were added to an aqueous solution of 50 g of water.
The mixture was added at 70-85°C for 3 hours, cooled, and extracted with benzene. Thereafter, it was treated once in the same manner as in Preparation Example 1, and 76 g of a white solid was obtained.

20 g of methanol was added to this and recrystallized by heating to obtain colorless needle-like crystals (trans form) of ethylisoeugenol in a yield of 85% (m, p, 64°C (trans form)).

Preparation Example 3 Preparation of benzylisoeugenol Sodium hydroxide2. 1 g (0,0525 mol)
and isoeugenol (manufactured by Wako Tsumugi Co., Ltd.) in an aqueous solution of 22 g of water.8. 21 g (0.05 mol) was added thereto, and further 0.25 g of trimethylaminopencyl chloride and 10.18 g (0.055 mol) of benzyl bromide were added, and the mixture was heated at 85 to 100°C for 3 hours.

After cooling the reaction solution, it was treated according to Preparation Example 1 described above to obtain 13.8 g of a yellow solid. Add this to 30g of ethanol
was added and heated and recrystallized to obtain colorless needle-like crystals of benzylisoeugenol (mixture of cis and trans forms) in a yield of 90% (trans form m, p, 57°C1 cis form m, p , 34°C).

Test Example 1 2.5% methylisoeugenol obtained in Preparation Example 1
Alternatively, a 0.6% acetone solution was used, and a miticide test was conducted on Dermatophagoides pectus mites.

The amount of active ingredients is 2. 0. 0. It was set to 5g/r+1'. The results are shown in Table 1.

The test method was conducted in accordance with the clip method (residue contact method) of the Ministry of Health and Welfare notification "Handling of tick control agents" (Pharmaceutical Examination Board No. 2 No. 84, February 18, 1986).

That is, a 5 cm x 10 cm filter paper (Nα5C manufactured by Toyo Roshi)
), drop 0.5 cc of each sample evenly onto the filter paper, let it air dry for about 1 hour, then place 20 test mites into a filter paper folded in half, and seal the 3 sides other than the fold with eyeball clips (51 mm). After 24 hours, the bag was opened, and the number of insects that turned upside down and the number of living and dead insects were counted, and the effectiveness was determined based on the rate of turning over and the rate of death and death relative to the number of mites tested. In addition, as a control group, filter paper onto which only acetone or white kerosene was dropped was used to examine the influence of the solvent.

Mortality rate (%) = Mortality rate after 48 hours Test Example 2 The methylisoeugenol obtained in Preparation Example 1 was dissolved in white kerosene, and a miticidal test against Dermatophagoides nigricans was conducted in the same manner as in Test Example 1. The results are shown in Table 1.

Test Example 3 A miticidal test against Dermatophagoides sinensis was carried out in the same manner as in Test Example 1 using a 3% acetone solution of Koyamaki wood oil. The results are shown in Table 1.

Test Examples 4 to 6 Eugenol (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.), isoeugenol (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.), and benzylisoeugenol (obtained in Preparation Example 3) were made into a 1 to 2% acetone solution, and Test Example 1 was prepared.
A miticidal test against Dermatophagoides mites was conducted in the same manner as above. The results are shown in Table 1.

Test Example 7 ~] O methylisoeugenol (obtained in Preparation Example 1),
Isoeugenol (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) and methyl eugenol (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) were used to prepare an acetone solution, and a miticidal test against woolly mites was conducted in the same manner as in Test Example 1.

The results are shown in Table 2.

Test Examples 11 to 14 Methylisoeugenol (obtained in Preparation Example 1),
Isoeugenol (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.), eugenol (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.), and ethyl isoeugenol (obtained in Preparation Example 2) were used to make an acetone solution, and a miticide test against stag beetle mites was conducted as in Test Example 1. I did the same thing. The number of stag beetle mites used in the test was 30 to 40.

The results are shown in Table 3.

Comparative Examples 1 to 6 Fenitrothion and permethrin were used as a 1 to 2% acetone solution, and acaricidal tests were carried out against Dermatophagoides mites, woolly mites, and stag beetle mites in the same manner as in Test Example 1.

The results are shown in Tables 1 to 3.

Table 1 Effect on Dermatophagoides nigricans [margins below] Table 2 Effects on woolly spider mites Table 3 Effects on stag beetle mites [margins below] [blanks below] Example 1 Mixing 0.5 parts of isoeugenol, chiralenz part and 92.5 parts of deodorized kerosene After dissolving and filling into an aerosol container and attaching the pulp part, 60 parts of a propellant (liquefied petroleum gas) is pressurized and filled through the valve part to obtain an aerosol mite control agent.

Example 2 3 parts of methyl eugenol, 96 parts of a mixture of diatomaceous earth/clay/talc, and 1 part or more of calcium stearate are uniformly mixed and pulverized to obtain a dust mite control agent.

Example 3 40 parts of benzyl isoeugenol, 55 parts of a diatomaceous earth/clay mixture, and 5 parts of polyoxyethylene nonylphenyl ether were uniformly mixed and ground to obtain a mite control agent in the form of a wettable powder.

Example 4 20 parts of eugenol, 20 parts of tetrahydrofuran, 45 parts of killene, and 15 parts of a mixture of polyoxyethylene nonylphenyl ether and alkylbenzene sulfonate are uniformly mixed and dissolved to obtain an emulsion of a mite control agent.

[Effects of the Invention] As shown in the results of the test examples, the mite control agent of the present invention has the same or higher effectiveness against organic phosphorus compounds and pyrethroid compounds against mites such as Dermatophagoides nigricans, woolly mites, and stag beetle mites. It has a mite control effect and is effective regardless of the type of mite, so it is useful for controlling indoor mites.

Moreover, the active ingredient of the mite control agent of the present invention has low toxicity and has a fragrance, so it has been used as a food additive fragrance for many years, and it is highly safe for the human body and can be safely used as a mite control agent. be able to.

Patent applicant: Tree Extract Component Utilization Technology Research Association Representative Patent Attorney: Yoshinori Hosoda (1 person)

Claims (2)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R represents a hydrogen atom, an alkyl group, or an aralkyl group. X is -CH_2-CH=CH_2 or -CH=
Represents CH-CH_3. A tick control agent containing a compound represented by ] as an active ingredient. (2) The content of the compound represented by the general formula is 0.1 to 4
The mite control agent according to claim 1, which contains 0% by weight.